Silk-based intelligent fibers and textiles: structures, properties, and applications.

Multifunctional fibers represent a cornerstone of human civilization, playing a pivotal role in numerous aspects of societal development. Natural biomaterials, in contrast to synthetic alternatives, offer environmental sustainability, biocompatibility, and biodegradability. Among these biomaterials, natural silk is favored in biomedical applications and smart fiber technology due to its accessibility, superior mechanical properties, diverse functional groups, controllable structure, and exceptional biocompatibility. This review delves into the intricate structure and properties of natural silk fibers and their extensive applications in biomedicine and smart fiber technology. It highlights the critical significance of silk fibers in the development of multifunctional materials, emphasizing their mechanical strength, biocompatibility, and biodegradability. A detailed analysis of the hierarchical structure of silk fibers elucidates how these structural features contribute to their unique properties. The review also encompasses the biomedical applications of silk fibers, including surgical sutures, tissue engineering, and drug delivery systems, along with recent advancements in smart fiber applications such as sensing, optical technologies, and energy storage. The enhancement of functional properties of silk fibers through chemical or physical modifications is discussed, suggesting broader high-end applications. Additionally, the review addresses current challenges and future directions in the application of silk fibers in biomedicine and smart fiber technologies, underscoring silk's potential in driving contemporary technological innovations. The versatility and sustainability of silk fibers position them as pivotal elements in contemporary materials science and technology, fostering the development of next-generation smart materials.

Advances of Layered Double Hydroxide-Based Materials for Tumor Imaging and Therapy.

Layered double hydroxides (LDH) are a class of functional anionic clays that typically consist of orthorhombic arrays of metal hydroxides with anions sandwiched between the layers. Due to their unique properties, including high chemical stability, good biocompatibility, controlled drug loading, and enhanced drug bioavailability, LDHs have many potential applications in the medical field. Especially in the fields of bioimaging and tumor therapy. This paper reviews the research progress of LDHs and their nanocomposites in the field of tumor imaging and therapy. First, the structure and advantages of LDH are discussed. Then, several commonly used methods for the preparation of LDH are presented, including co-precipitation, hydrothermal and ion exchange methods. Subsequently, recent advances in layered hydroxides and their nanocomposites for cancer imaging and therapy are highlighted. Finally, based on current research, we summaries the prospects and challenges of layered hydroxides and nanocomposites for cancer diagnosis and therapy.

Fabrication of polyethyleneimine functionalized magnetite nanoparticles for recyclable recovery of fucoidan from aqueous solution.

Fucoidan is a kind of natural water-soluble fucose-rich sulfated polysaccharide with promising applications in the food and pharmaceutical industry. However, the traditional methods for fucoidan recovery from aqueous solution are expensive, time-consuming, and environmentally unfriendly. In this work, polyethyleneimine functionalized magnetite nanoparticles (PEI-MNPs) with well-defined core-shell structures were prepared by a Layer-by-Layer (LbL) approach using sodium tripolyphosphate (STPP) as a cross-linker. The as-prepared PEI-MNPs showed improved adsorption capability towards fucoidan at pH 4-8 due to the high density of cationic groups on the surfaces and the absence of internal pores. It was found that the adsorption process of fucoidan onto PEI-MNPs can reach to equilibrium in 50 min at room temperature. The maximum qe derived from the Langmuir isotherm at room temperature was 169.1 mg per g at a pH of 7. A selective fucoidan capture over a model protein BSA can be realized by adjusting pH (6-8) and salt concentration (0.5-2.5 M). The PEI-MNPs loading with fucoidan can be isolated from the final products by a neodymium magnet and regenerated by 4 M NaCl solution as stripping reagent. Therefore, this novel kind of PEI-MNP could be a promising candidate for highly efficient and recyclable recovery of fucoidan from an aqueous solution.

mRNA therapeutics for disease therapy: principles, delivery, and clinical translation.

Messenger RNA (mRNA) has become a key focus in the development of therapeutic agents, showing significant potential in preventing and treating a wide range of diseases. The COVID-19 pandemic in 2020 has accelerated the development of mRNA nucleic therapeutics and attracted significant investment from global biopharmaceutical companies. These therapeutics deliver genetic information into cells without altering the host genome, making them a promising treatment option. However, their clinical applications have been limited by issues such as instability, inefficient in vivo delivery, and low translational efficiency. Recent advances in molecular design and nanotechnology have helped overcome these challenges, and several mRNA formulations have demonstrated promising results in both animal and human testing against infectious diseases and cancer. This review provides an overview of the latest research progress in structural optimization strategies and delivery systems, and discusses key considerations for their future clinical use.

Controllable formation of amorphous structure to improve the oxygen evolution reaction performance of a CoNi LDH.

The morphology design of layered double hydroxides (LDHs) is an important way to determine the catalytic performance of LDH materials. A novel structure of CoNi LDH sheets with amorphous structure on the edge was prepared by electrooxidation. It was characterized by XRD, SEM, TEM and XPS. It was found that during the electrooxidation, some of the Co2+ ions were oxidized to Co3+ to form amorphous CoOOH intermediates, which promoted the OER performance. The electrochemical test results show that CoNi LDH treated by electrooxidation for 6 hours has an ultra-low overpotential of 206 mV at a current density of 10 mA cm-2, and can work stably under alkaline conditions for more than 10 hours. This work suggests that introducing an amorphous structure on LDH through electrooxidation produces abundant active sites, which is an easy and efficient method to improve the OER performance of CoNi LDHs.

An Investigation of Non-Linear Strength Characteristics of Solidified Saline Soils in Cold Regions.

To date, the modelling of constitutive equations of solidified frozen saline soil have seldom been studied. This paper presented the formulation of a damage constitutive model for solidified saline frozen soil considering both freeze thaw cycles (FTCs) and salinities. To model the solidified frozen saline soil, the unconfined compression strength test (UCST) and consolidated undrained (CU) triaxial shear test were conducted under three ambient temperatures (20, -10, and -20 °C), five ages (3, 7, 14, 28, and 90 d), six salinities (0, 1, 2, 3, 4, and 5%), and four FTCs (0, 5, 10, and 14 times) in this research. The UCST results showed that the unconfined compressive strength (UCS) of the solidified saline soils at an age of 14 days can reach 75% of the maximum UCS, which basically meets the engineering construction requirements. The range of the rate of strength loss as affected by salinity was 16.2% to 75.65%, while the coupling effect of salt and frozen conditions amplified the rate of strength loss. Affected by increasing salinity, the rate of strength loss of frozen soils was magnified by a factor of 1.2 to 3.7 compared to thawing soils. Likewise, the CU triaxial shear test showed that the rate of strength loss of shear strength was amplified by the coupling effect of FTCs and salt erosion. With increased FTCs, the strain threshold of Young's modulus was gradually pushed backward, which was similar to the effect of salinity. Remarkably, the damage constitutive model performed better than conventional constitutive models for the solidified saline soil under the salt-freezing coupling effect.

Point-of-care non-invasive enzyme-cleavable nanosensors for acute transplant rejection detection.

Accurate and non-invasive monitoring of allograft posttransplant is essential for early detection of acute cellular rejection and determines the long-term survival of the graft. Clinically, tissue biopsy is the most effective approach for diagnosing transplant rejection. Nonetheless, the procedure is invasive and potentially triggers organ failure. This work aims to design and apply GzmB-responsive nanosensors (GBRNs) that can readily size-change in graft tissues. Subsequently, we investigate the activity of serine protease granzyme B by generating a direct colorimetric urinary readout for non-invasive detection of transplant rejection in under 1 h. In preclinical heart graft mice models of transplant rejection, GBRNs were cleaved by GzmB and excreted by the kidneys via accurate nanometre-size glomerular filtration. By exploiting the catalytic activity of ultrasmall gold nanoclusters, GBRNs urinalysis promotes ultrasensitive surveillance of rejection episodes with a receiver operator characteristic curve area under the curve of 0.896 as well as a 95% confidence interval of about 0.7701-1.000. Besides, the catalytic activity of gold nanoclusters in urine can be detected at point-of-care testing to predict the immunity responses in mice with insufficient immunosuppressive therapy. Therefore, this non-invasive, sensitive, and quantitative method is a robust and informative approach for rapid and routine monitoring of transplant allografts without invasive biopsy.

A photocontrollable thermosensitive chemical spatiotemporally destabilizes mitochondrial membranes for cell fate manipulation.

Perturbations in mitochondrial membrane stability lead to cytochrome c release and induce caspase-dependent apoptosis. Using synthetic smart chemicals with changeable physicochemical properties to interfere the mitochondrial membrane stability has not yet been reported. Here we show that a thermosensitive anchor-polymer-peptide conjugate (anchor-PPC) destabilizes mitochondrial membranes upon in situ molecule changes from hydrophilic to hydrophobic, which consequently induces apoptosis in a spatiotemporally controlled manner and acts as an antitumor pharmaceutical. The anchor-PPC is composed of a thermosensitive copolymer, a photolabile linker, a hydrophilic HIV Tat-derived peptide both for cell penetration and polymer phase transition temperature (Tt) modulation, and an anchor peptide for intercalating into mitochondrial membranes. The photocontrollable anchor-PPC dehydrates and changes from being hydrophilic to hydrophobic upon photoactivation at body temperature. This cell-penetrable anchor-PPC specifically targets mitochondria and destabilizes mitochondrial membranes upon irradiation, and consequently initiates apoptosis in cells and a complex 3D tumor model. This study provides the first experimental evidence that the synthetic smart chemical can spatiotemporally control the stability of organelle membranes based on its in situ physicochemical property change.

CuCoFe Layered double hydroxides as laccase mimicking nanozymes for colorimetric detection of pheochromocytoma biomarkers.

A laccase catalyzed colorimetric biosensing approach is promising for the detection of pheochromocytoma biomarkers, yet suffers from the poor stability of enzymes and high cost for production. Here we report for the first time an easy to produce, cheap, stable and reliable laccase-mimicking CuCoFe-LDHzyme, which can catalyze the oxidation of pheochromocytoma biomarkers to form a chromogenic product for smartphone-based colorimetric detection.

Water-soluble PANI:PSS designed for spontaneous non-disruptive membrane penetration and direct intracellular photothermal damage on bacteria.

The major challenge in the field of antibacterial agents is to overcome the low-permeability of bacteria cell membranes that protects the cells against diverse drugs. In this work, water-soluble polyaniline (PANI)-poly (p-styrenesulfonic acid) (PSS) (PANI:PSS) is found to spontaneously penetrate bacteria cellular membranes in a non-disruptive way, leaving no evidence of membrane poration/disturbance or cell death, thus avoiding side effects caused by cationic ammonia groups in traditional ammonia-containing antibacterial agents. For aqueous synthesis, which is important for biocompatibility, the polymer is synthesized via an enzyme-mimetic route relying on the catalysis of a nanozyme. Owing to its fluorescent properties, the localization of as-prepared PANI:PSS is determined by the confocal microscope, and the results confirm its rapid entry into bacteria. Under 808 nm near-infrared (NIR) irradiation, the internalized PANI:PSS generates local hyperthermia and destroys bacteria highly efficiently from inside the cells due to its excellent photothermal effects. Staphylococcus aureus (S. aureus), M ethicillin-resistant Staphylococcus aureus (MRSA) and Escherichia coli (E. coli) could be effectively eliminated as well as the corresponding bacterial biofilms. Results of in vivo antibacterial experiments demonstrate excellent antibacterial activities of the water-soluble PANI:PSS without side effects. Therefore, the prepared water-soluble polymer in this study has great potential in the treatment of various bacterial infections.

Effective Antibacterial Activity of Degradable Copper-Doped Phosphate-Based Glass Nanozymes.

Copper-containing antimicrobials are highly valuable in the field of medical disinfectants owing to their well-known high antimicrobial efficacy. Artificially synthesized nanozymes which can increase the level of reactive oxygen species (ROS) in the bacterial system have become research hotspots. Herein, we describe the design and fabrication of degradable Cu-doped phosphate-based glass (Cu-PBG) nanozyme, which can achieve excellent antibacterial effects against Gram-positive and Gram-negative bacteria. The antibacterial mechanism is based on the generation of ROS storm and the release of copper. It behaves like a peroxidase in wounds which are acidic and exerts lethal oxidative stress on bacteria via catalyzing the decomposition of H2O2 into hydroxyl radicals (•OH). Quite different from any other reported nanozymes, the Cu-PBG is intrinsically degradable due to its phosphate glass nature. It gradually degrades and releases copper ions in a physiological environment, which further enhances the inhibition efficiency. Satisfactory antibacterial effects are verified both in vitro and in vivo. Being biodegradable, the prepared Cu-PBG exhibits excellent in vivo biocompatibility and does not cause any adverse effects caused by its long-time residence time in living organisms. Collectively, these results indicate that the Cu-PBG nanozyme could be used as an efficient copper-containing antimicrobial with great potential for clinical translation.

Nitrogen- and Oxygen-Containing Three-Dimensional Hierarchical Porous Graphitic Carbon for Advanced Supercapacitor.

Three-dimensional hierarchical porous graphitic carbon (HPGC) were synthesized via one-step carbonization-activation and a catalytic strategy. The method can not only improve the graphitization degree of carbon materials, but also offer plentiful interfaces for charge accumulation and short paths for ion/electron transport. Polypyrrole, potassium hydroxide, and nickel acetate were used as the carbon precursors, activating agent, and catalyst, respectively. The retraction and dissolution of Ni caused the change of pore size in the material and led to the interconnected micro/nano holes. Nickel acetate played a significant role in enhancing the electrical conductivity, introducing pseudocapacitance, and promoting ion diffusion. In the supercapacitor, HPGC electrode exhibited a remarkable specific capacitance of 336.3 F g-1 under 0.5 A g-1 current density and showed high rate capability, even with large current densities applied (up to 50 A g-1). Moreover, HPGC showed optimal cycling stability with 97.4% capacitance retention followed by 3000 charge-discharge cycles. The excellent electrochemical performances coupled with a facile large-scale synthesis procedure make HPGC a promising alternative for supercapacitors.

Preparation and properties of a highly dispersed nano-hydroxyapatite colloid used as a reinforcing filler for chitosan.

Hydroxyapatite/chitosan (HAp/CS) composites have been widely studied and applied in tissue engineering fields due to their excellent biocompatibility and degradability. However, to improve the mechanical properties of CS, cross-linking agents are commonly added, which will seriously affect its biocompatibility and safety. In this study, the homogenously dispersed nano-hydroxyapatite (nHAp) colloidal solution was first synthesized using a co-precipitation method. The three-dimensional porous nano-hydroxyapatite/chitosan (nHAp/CS) composite scaffolds with different nHAp contents were then obtained through an environmentally friendly freeze-drying process without any cross-linking. The microstructure, porosity, phase composition, swelling ratio, mechanical properties, and biocompatibility of the nHAp/CS scaffolds were thoroughly investigated. The as-prepared nHAp/CS scaffolds exhibited a high porosity and excellent swelling performance. Compared with pure CS scaffolds, the nHAp/CS composite scaffolds not only showed higher compressive modulus but also exhibited better biocompatibility. This study provides a simple and environmentally friendly technique to construct three-dimensional porous nHAp/CS composite scaffolds, which demonstrate promising potential by being a scaffold material for bone tissue engineering.

Tailoring magnetic resonance imaging relaxivities in macroporous Prussian blue cubes.

In order to unravel the relationship between zeta potential values and r2/r1 ratios for contrast agents in MRI application, a series of macroporous Prussian blue cubes were successfully synthesized by HCl etching and used as model samples for relaxivity investigation. It was found that their r2/r1 ratios firstly decreased and then increased with the increasing HCl concentration, while the variation trend for zeta potential is quite the opposite. By employing Gauss fitting and eliminating the HCl concentration in the resultant equations, a relationship between zeta potential values and r2/r1 ratios, i.e. ζ = 229 × (563 -r2/r1)0.012- 267, was finally obtained. This result showed that magnetic resonance imaging relaxivities (viz. r2/r1) could be tailored through altering zeta potential values (surface charges) of the contrast agent.

Anticancer Effects and Cell Death Pathways in Ultralow-Power 980 nm Laser-Triggered Photodynamic Therapy by Gd2O3:Yb, Tm Nanoparticles.

Upconverting Gd2O3:Yb, Tm nanoparticles that can provide photodynamic therapy (PDT) for cancer cells upon 980 nm near-infrared (NIR) laser irradiation are prepared. The nanoparticles emit bright blue upconversion fluorescence (470∼520 nm) when excited by a 980 nm laser. A well-selected PDT drug, merocyanine 540 (MC540), which shows an absorption maximum within the 495∼540 nm band, is loaded onto the surface of the nanoparticles to obtain Gd2O3:Yb, TmMC540. A prominent PDT-induced killing effect on both human cervical cancer cells (HeLa cells) and human hepatocellular liver carcinoma cells (HepG2 cells) is achieved under 980 nm laser irradiation at a very low power density of 0.65 W cm-2, which is lower than The American National Standard for the safe use of 980 nm lasers (0.72 W cm-2. The cell death modes are further studied in detail via a uranyl acetate section-staining method to analyze the morphological cell changes before and after PDT. With clear evidence of mitochondrial damage, chromatin condensation and the formation of apoptotic bodies, an apoptosis mechanism is confirmed to be responsible for both HeLa and HepG2 cell death in Gd2O3:Yb, Tm-MC540-mediated PDT. Due to excessive damage, the cancer cells are efficiently killed, and autophagy is found to be initiated immediately after PDT.

Preparation of core-shell structured metal-organic framework@PANI nanocomposite and its electrorheological properties.

A novel core-shell-type electrorheological (ER) composite material was fabricated via using polyaniline as an insulating layer to the outer surface of the core conductive metal-organic framework (MIL-125) with controlled size and morphology. MIL-125 was firstly synthesized by a solvothermal method, and then polyaniline was synthesized in a polar solvent and a tight coating was successfully achieved to form a MIL-125@PANI core-shell nanocomposite. This core-shell structure greatly enhances the polarization ability of dispersed particles, thereby improving their rheological properties. The morphology of pure MIL-125 and MIL-125@PANI has been characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Their structure was characterized by X-ray powder diffraction. Moreover, the ER activity of MIL-125-based and MIL-125@PANI-based ER fluids by dispersing the particles into silicone oil was studied using a rotational rheometer. The results show that the MIL-125@PANI composite particles have higher ER properties.

Impact of metallic trace elements on relaxivities of iron-oxide contrast agents.

In this work, well-defined 3 nm-sized Ca2+, Fe3+, Na+, Mg2+, Zn2+, Ni2+, Co2+, and Cd2+ cation-adsorbed Fe3O4/γ-Fe2O3 nanoparticles were used as prototype systems to investigate the influence of metallic trace elements in body fluids on the relaxivities of iron-oxide contrast agents. It was found that surface-adsorbed cations formed a deterioration layer to induce pronounced relaxivity loss. Theoretical study showed that such relaxivity loss can be well described by a modified GCAS function, taking into account the harmonic cation oscillations around Fe3O4/γ-Fe2O3 nanoparticles. Quantum mechanics analyses revealed that even-parity and odd-parity states of harmonic oscillations are dominant in r 1 and r 2 relaxivities, respectively. Moreover, the harmonic oscillations of Na+ and Mg2+ cations around Fe3O4/γ-Fe2O3 nanoparticles are found to be classical forbidden, which are quite different from their counterparts located in the classical permissive area.

The preparation and electrorheological behavior of bowl-like titanium oxide nanoparticles.

Bowl-like titanium oxide nanoparticles were successfully prepared by a simple solvothermal method using absolute ethanol and isopropanol as the cosolvent. Ostwald ripening coupled with the inner-stress-induce effect were assumed to play an important role in the formation of this unique bowl-like morphology. The morphological evolution from solid nanosphere to bowl-like nanoparticle was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Besides, the structural characteristics of the as-synthesized TiO2 nanoparticles were confirmed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and thermogravimetric analysis (TGA). Moreover, a rotational rheometer was operated to examine the electrorheological (ER) effect. Excellent ER properties were achieved when the TiO2 particles were dispersed in silicone oil under an external electric field.

Synthesis of anatase TiO2 with exposed (100) facets and enhanced electrorheological activity.

Herein, a simple hydrothermal method is employed to synthesize anatase TiO2 with dominant (100) facets, as a precursor, using titanate nanofibers derived from alkali treatment. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) are carried out to confirm the surface morphology and phase structure of the TiO2 product. The formation mechanism of TiO2 enclosed by (100) and (101) facets is deduced to be the selective adsorption of OH- on the (100) facets of anatase TiO2. Electroheological (ER) experiments indicate that the tetragonal-facet-rod anatase TiO2 with exposed (100) facets exhibits an excellent ER performance with a high ER efficiency of up to 52.5, which results from the anisotropy of its special morphology. In addition, the effect of shape on its dielectric property is investigated via broadband dielectric spectroscopy.

Facile and scalable synthesis of magnetite/carbon adsorbents by recycling discarded fruit peels and their potential usage in water treatment.

In this study, apple, banana and orange peels were used as precursor compounds for the mass production of magnetite/carbon adsorbents. A so-called "soak-calcination" procedure was employed by firstly soaking these waste fruit peels in FeCl3 aqueous solutions and secondly calcining these precursors in the nitrogen atmosphere to yield final magnetite/carbon composites. This approach is quite simple and effective to synthesize carbon-based adsorbents on an industrial scale. The as-produced adsorbents feature the merits of appropriate ferromagnetism (>4emug-1), high adsorption capacity (several hundreds of milligrams per gram for adsorption of methyl blue, Congo red, rhodamine B and Cr6+ ions), and good regenerability (>85%).